WO2017148750A1 - Composition d'un agent antimousse pour un détergent - Google Patents

Composition d'un agent antimousse pour un détergent Download PDF

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Publication number
WO2017148750A1
WO2017148750A1 PCT/EP2017/053946 EP2017053946W WO2017148750A1 WO 2017148750 A1 WO2017148750 A1 WO 2017148750A1 EP 2017053946 W EP2017053946 W EP 2017053946W WO 2017148750 A1 WO2017148750 A1 WO 2017148750A1
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Prior art keywords
units
formula
defoamer
radical
sum
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PCT/EP2017/053946
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German (de)
English (en)
Inventor
Holger Rautschek
Richard Becker
Christof Brehm
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Wacker Chemie Ag
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Application filed by Wacker Chemie Ag filed Critical Wacker Chemie Ag
Priority to EP17707502.5A priority Critical patent/EP3423165B1/fr
Priority to KR1020187025075A priority patent/KR102142380B1/ko
Priority to CN201780014634.4A priority patent/CN108778443B/zh
Priority to US16/081,789 priority patent/US10870732B2/en
Priority to JP2018545958A priority patent/JP6816159B2/ja
Publication of WO2017148750A1 publication Critical patent/WO2017148750A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/162—Organic compounds containing Si
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups

Definitions

  • the invention relates to antifoam compositions containing specific polysiloxanes and polyethers, and their use for defoaming aqueous media, in particular aqueous
  • foaming may cause problems if these systems are brought into more or less intensive contact with gaseous substances, for example when fumigating waste water, during intensive Stirring liquids, during distillation, washing or dyeing processes or during filling operations.
  • the control of this foam can be done by mechanical means or by the addition of defoamers.
  • Defoamers based on siloxanes have proven particularly useful. Defoamers based on siloxanes, for example, according to DE-AS 15 19 987 by heating hydrophilic silica in
  • Liquid detergents based on branched high-viscosity Counteract siloxanes (EP 499364 Bl, EP 635564 AI).
  • polyether siloxanes (US 4,983,316 A), the
  • antifoam compositions comprising a defoamer compound comprising liquid polyorganosiloxanes having aromatic radicals bonded directly to silicon, silicone resins and / or fillers, and defined polyethers and optionally polyethersiloxanes.
  • the invention provides antifoam compositions containing
  • R 1 may be the same or different and a
  • R 2 may be the same or different and one
  • Hydrocarbon radical which is attached via a ring carbon atom to the silicon atom, means
  • a 0, 1, 2 or 3
  • b 0, 1, 2 or 3 and
  • c 0, 1, 2 or 3
  • the sum a + b + c is less than or equal to 3 and in 1-100%, preferably in 10-60%, particularly preferably in 20-40%, of all units of the formula (I) c is different 0 and in at least 50% of all units of formula (I) in the organosilicon compound the sum a + b + c is equal to 2,
  • (a21) filler particles preferably silica
  • Silicas titanium dioxide or alumina, and / or
  • R 3 may be the same or different and a
  • R 4 Denotes a hydrogen atom or a monovalent, optionally substituted, SiC-bonded hydrocarbon radical, R 4 may be the same or different and one
  • d 0, 1, 2 or 3
  • e 0, 1, 2 or 3
  • R 5 may be the same or different and has a meaning given for R
  • R s may be the same or different and has a meaning given for R 1 ,
  • g 0, 1, 2 or 3 and
  • h 0, 1, 2 or 3
  • radicals R are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert.
  • -Pentyl radical hexyl radicals, such as the n-hexyl radical, heptyl radicals, such as the n-heptyl radical, octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2, 2, 4-trimethylpentyl radical, nonyl radicals, such as the n-nonyl radical , Decyl radicals, such as the n-decyl radical, dodecyl radicals, such as
  • n-dodecyl radical Alkenyl radicals, such as the vinyl and allyl radicals; Cycloalkyl radicals, such as cyclopentyl, cyclohexyl, cycloheptyl radicals and methylcyclohexyl radicals, aromatic groups bonded to the siliconator via aliphatic groups, such as
  • substituted radicals R are 3, 3, 3-trifluoro-n-propyl radical, cyanoethyl, glycidoxy-n-propyl, polyalkylene glycol-n-propyl, amino-n-propyl, aminoethylamino-n-propyl and methacryloxy-n-propyl radicals.
  • the radical R is a hydrogen atom or a monovalent, optionally substituted, aliphatic hydrocarbon radical having 1 to 30 carbon atoms, preferably a monovalent aliphatic hydrocarbon radical having 1 to 4 carbon atoms, in particular the methyl radical.
  • radical R 1 are the hydrogen atom and the radicals indicated for radical R and R 2 .
  • the radical R 1 is a hydrogen atom or a monovalent, optionally substituted Hydrocarbon radical having 1 to 30 carbon atoms, preferably a hydrogen atom or a monovalent hydrocarbon radical having 1 to 4 carbon atoms, in particular the methyl or ethyl radical.
  • R 2 examples include aryl radicals, such as phenyl, tobolyl, xylyl, cumyl, naphthyl and anthracyl radicals.
  • the radical R 2 is preferably the phenyl radical.
  • radical R 3 are the hydrogen atom and the radicals indicated for radical R and R 2 .
  • the radical R 3 is a monovalent, optionally substituted hydrocarbon radical having 1 to 30 carbon atoms, preferably a monovalent
  • Hydrocarbon radical having 1 to 6 carbon atoms
  • radical R 4 are the radicals specified for the radical R 1 .
  • the radical R 4 is a hydrogen atom or a monovalent hydrocarbon radical having 1 to 4 carbon atoms, in particular a hydrogen atom or the methyl or ethyl radical.
  • the value of d is 3 or 0.
  • radicals R 5 are those indicated for radical R.
  • the radical R s is preferably a hydrogen atom or a monovalent, optionally substituted, aliphatic hydrocarbon radical having 1 to 30 carbon atoms, preferably a monovalent aliphatic hydrocarbon radical having 1 to 4 carbon atoms, in particular the methyl radical.
  • radical R 6 are the hydrogen atom and the radicals given for radical R and R 2.
  • the radical R e is a hydrogen atom or a monovalent, optionally substituted hydrocarbon radical having 1 to 30 carbon atoms, preferably a hydrogen atom or a monovalent hydrocarbon radical having 1 to 4 carbon atoms, in particular the methyl or ethyl radical.
  • Component (A) contains a polyorganosiloxane (al), the
  • the organosilicon compounds (al) are selected from the organosilicon compounds (al)
  • Organopolysiloxanes consisting of units of the formula (I).
  • Examples of the component (a1) are those containing one or more units of the formulas
  • Ph 3 SIOI / 2 -, Ph 2 MeSi0 1/2 - PhSi0 3/2, and - - contain, PhMe 2 SIOI / 2 -, Ph 2 Si0 2/2 - 2/2 PhMeSi0
  • the organosilicon compounds (a1) have a viscosity of preferably from 10 to 1,000,000 mPas, more preferably from 100 to 50,000 mPas, in particular from 500 to 5,000 mPas, each measured at 25 ° C. and a shear rate of 1 / s.
  • the organosilicon compounds (al) are commercially available
  • Component (a21) is preferably
  • Component (a21) preferably has a BET surface area of from 20 to 1000 m 2 / g, a particle size of less than 10 ⁇ m, and an agglomerate size of less than 100 ⁇ m.
  • component (a21) examples are silica
  • component (a21) Particle size of less than 10 ⁇ and an agglomerate size of less than 100 ⁇ used.
  • Particularly preferred as component (a21) are silicic acids, more preferably those having a BET surface area of 50 to 800 m 2 / g, in particular those having a BET surface area of 80 to 500 m 2 / g. These silicas may be fumed or precipitated silicas. There are as component (a21) both
  • pretreated silicas used ie commercially available hydrophobic silicas, as well as hydrophilic silicas.
  • the degree of hydrophobization is determined by the number of methanol
  • hydrophobic silicas are preferably
  • hydrophobic silicas which can be used according to the invention, HDK ® H2000, a fumed treated Hexamethyldisilazanen silica having a BET surface area of 140 m 2 / g (commercially available from Wacker Chemie AG, Kunststoff, Germany) and precipitated with
  • hydrophobic silicas are to be used as component (a21), hydrophilic silicas can also be rendered hydrophobic in situ if this is advantageous for the desired activity of the antifoam formulation.
  • Hydrophobization of silicas are widely known.
  • the in situ hydrophobing of the hydrophilic silica can be z. B. by heating for several hours in the component (al) dispersed silica to temperatures of 100 to 200 ° C. In this case, the reaction by the addition of
  • Catalysts such as KOH, and water repellents, such as short-chain OH-terminated polydimethylsiloxanes, silanes or silazanes are supported. This treatment is also possible with the use of commercially available hydrophobic silicic acids and can contribute to improving the efficacy.
  • Fillers (a22) are used in the defoamer formulations according to the invention preferably in amounts of at least 1% by weight and at most 20% by weight, preferably at most 10% by weight, based in each case on the total weight of the defoamer compound (A).
  • Component (a22) is particularly preferably organopolysiloxane resins which consist essentially of R 3 3 SiO 2 / M 2 and Si0 4/2 (Q) units, where R 3 has the meaning given above. These resins are also referred to as MQ resins.
  • the molar ratio of M to Q units is preferably in the range of 0.5 to 2.0, more preferably in the range of 0.6 to 1.0.
  • These silicone resins can also be up to 10% by weight of Si-bonded hydroxy or alkoxy groups.
  • R 3 is preferably a methyl radical.
  • the organopolysiloxane resins (a22) at 25 ° C have a viscosity greater than 1000 mPas or are solids.
  • Molecular weight (based on a polystyrene standard) of these resins is preferably 200 to 200,000 g / mol, in particular 1,000 to 20,000 g / mol.
  • the organopolysiloxane resins (a22) used according to the invention are preferably soluble in benzene at a temperature of 25 ° C. and a pressure of 101.325 kPa to at least 100 g / l.
  • Siloxane resins (a22) are preferably used in the defoamer formulations according to the invention in amounts of at least 1% by weight and at most 20% by weight, preferably at most 10% by weight, based in each case on the total weight of the defoamer compound (A).
  • Organosilicon compounds (a3) Organopolysiloxanes consisting of units of the formula (III).
  • the optionally used organopolysiloxanes (a3) have a viscosity of preferably 10 to 1 000 000 mm 2 / s at 25 ° C.
  • Organopolysiloxanes (a3) are those which differ from
  • Organopolysiloxanes (al) are and contain no directly attached to silicon aromatic radicals, such as
  • These branched or cross-linked siloxanes then have viscoelastic properties.
  • the optionally used component (a3) is preferably substantially linear organopolysiloxanes containing units of the formula (III), particularly preferably polydimethylsiloxanes which react with silanol groups and / or with
  • Such products are accessible, for example, by alkaline-catalyzed condensation of silanol-terminated polydimethylsiloxanes having a viscosity of from 50 to 50,000 mPa.s at 25 ° C.
  • aliphatic alcohols having more than 6 carbon atoms such as isotridecyl alcohol, n-octanol, stearyl alcohol, ethylhexadecanol or eicosanol.
  • compositions according to the invention contain component (a3), these are amounts of preferably 1 to 90
  • Wt .-% particularly preferably 2 to 50 wt .-%, in particular 2 to 10 wt .-%, each based on the total weight of
  • the antifoam formulations according to the invention preferably contain 10-90% by weight, more preferably 20-80% by weight, in particular 30-70% by weight, of components (A).
  • Components (B) are preferably polyoxyalkylenes of the formula R 7 - [O-CH 2 -CH (CH 3 )] K - [O-CH 2 -CH 2 ] y -O-R 7 (IV) wherein R 7 may be the same or different and a hydrogen atom, a Ci -C 30 alkyl group, a Ci-C 30 alkenyl radical or a radical of the formula R 8 -C (0) - (V)
  • R 8 denotes a C 1 -C 22 -alkyl radical
  • y has a value from 0 to 30
  • radicals R 7 are the hydrogen atom and the
  • Methyl, allyl and butyl radical are preferably, the radical R 7 is a hydrogen atom.
  • radicals of the formula R 8 are the methyl and
  • the index x is preferably 15 to 150, preferably 25 to 100.
  • the polyoxyalkylenes of the formula (IV) preferably have an average molar mass (number average Mn) of from 100 to
  • the polyoxyalkylenes used are preferably polypropylene glycols having an average molar mass (number average Mn) of from 100 to 8000 g / mol.
  • polyoxyalkylenes (B) or more kinds of polyoxyalkylenes (B) can be used.
  • the oxyalkylene groups may be randomly distributed in the polyoxyalkylenes of the formula (I) or as block copolymers
  • Polyoxyalkylenes of the formula (IV) are known commercially available products. Depending on the values for x and y, the polyoxyalkylenes are liquids or waxy products, with liquid
  • Products with a viscosity (at 25 ° C and 1013 hPa) of 100 to 1500 mm 2 / s are preferred.
  • the solubility of the polyoxyalkylenes in water is determined by the ratio of y / x. Preference is given to using polyoxyalkylenes which are soluble in water at less than 2% by weight at 25 ° C. and 1013 hPa, or a cloud point (measured to EN 1890 variant A) of less than 35 ° C., in particular less than 25 ° C have.
  • the antifoam formulations according to the invention preferably contain 10-90% by weight, more preferably 20-80% by weight, in particular 30-70% by weight, of components (B).
  • Substances used as component (B) are commercial products.
  • polyether-modified siloxanes (C) it is preferred to use polyether-polysiloxane copolymers, which may be linear or branched polymers. Such polyether-polysiloxane copolymers are state of the art
  • linear polyether-polysiloxane copolymers are those in which the polyether radicals are linear to linear Siloxane chains via hydrocarbon radicals, preferably divalent hydrocarbon radicals, SiC-bonded.
  • Such linear polyether-polysiloxane copolymers are, for. B. in GB 2 350 117 A described.
  • branched polyether-polysiloxane copolymers are those in which the polyether radicals are bonded to linear siloxane chains laterally via hydrocarbon radicals, preferably bivalent hydrocarbon radicals, SiC-bonded and these linear siloxane chains are linked to one another via lateral organic bridges.
  • organic bridges are SiC-bonded linear or branched organic radicals, preferably
  • divalent hydrocarbon radicals which are one or more
  • Heteroatoms selected from the group of oxygen and
  • nitrogen atoms such as alkylene radicals, SiC-bonded polyether radicals, via the alkylene radicals to the
  • Siloxane chains are bonded, and SiC-bonded bivalent hydrocarbon radicals, such as alkylene radicals containing polyether and urethane groups.
  • Preferred branched polyether-polysiloxane copolymers used are those in which the siloxane chains are linked to one another via pendant bivalent SiC-bonded hydrocarbon radicals which contain polyether radicals and urethane groups.
  • the polyether-polysiloxane copolymers (C) can be used in the following
  • Defoamer compositions according to the invention preferably in amounts of 0 to 60 wt .-%, preferably 0 to 40 wt .-%,
  • Defoamer composition can be used.
  • compositions according to the invention may contain all other substances which have hitherto been used in antifoam formulations, e.g. organic compounds (D).
  • the optionally used component (D) is particularly preferably organic compounds having a boiling point greater than 100 ° C, at the pressure of the surrounding atmosphere, ie at 900 to 1100 hPa, in particular to
  • the organic compounds (D) can be used in the antifoam compositions according to the invention preferably in amounts of from 0 to 60% by weight, preferably 0 to 20% by weight, in particular 1 to 20% by weight, based in each case on the total weight of
  • Defoamer composition can be used.
  • Defoamer compositions according to the invention contain prefers no component (D).
  • water (E) is preferably used in amounts of at most 5% by weight, preferably at most 1% by weight, based in each case on the
  • the antifoam compositions of the invention preferably contain no addition of water, i. the concomitant use of water in the inventive is preferred
  • additives (F) it is possible to use all known additives selected from organic thickening polymers, preservatives, dyes and fragrances.
  • alkaline catalysts are alkali and alkaline earth hydroxides, such as NaOH, KOH, CsOH, LiOH and Ca (OH) 2 .
  • acidic catalysts are hydrochloric acid, sulfuric acid and phosphonitrile chlorides.
  • the dosing of the catalysts may be carried out in typical organic solvents such as alcohols (such as methanol, ethanol,
  • the antifoam compositions according to the invention preferably consist of
  • compositions according to the invention are preferably viscous, clear to opaque, as well as colorless to brownish liquids.
  • compositions of the invention have a viscosity of preferably 1 to 20,000 mPas, more preferably from 5 to 5000 mPas, in particular from 10 to 2000 mPas, each at 25 ° C and a shear rate of 1 / s.
  • compositions according to the invention may be solutions or dispersions.
  • preparation of the compositions of the invention may be carried out by known methods, e.g. by mixing all
  • Components are made, e.g. by simple stirring with static mixers or even by using high
  • Another object of the present invention are to provide a third object of the present invention.
  • Surfactant formulations preferably wetting, washing and
  • Cleaning agent preferably at 20 ° C liquid wetting, washing and cleaning agents, especially liquid detergents, containing the compositions of the invention.
  • Another object of the present invention is a method for defoaming and / or foam prevention of media, characterized in that the inventive
  • Composition is mixed with the medium.
  • foaming media can be made directly in suitable
  • Solvents such as toluene, xylene, methyl ethyl ketone or tert. Butanol, dissolved, or as a powder.
  • the amount necessary to achieve the desired defoamer effect depends, for example, on the type of medium, the temperature and the
  • compositions of the invention are directly treated with concentrated liquid surfactant formulations, e.g. liquid detergents, mixed.
  • concentrated liquid surfactant formulations e.g. liquid detergents
  • the compositions according to the invention are preferably added in amounts of from 0.1 ppm by weight to 1% by weight, in particular in amounts of from 1 to 100 ppm by weight, to the ready-to-use foaming medium.
  • concentrated surfactant formulations such as liquid detergents
  • the inventive method is carried out at temperatures of preferably -10 to + 150 ° C, more preferably 5 to 100 ° C, and the pressure of the surrounding atmosphere, that is about 900 to 1100 hPa.
  • the process according to the invention can also be carried out at higher or lower pressures, such as at 3000 to 4000 hPa or 1 to 10 hPa.
  • the antifoam compositions according to the invention can be used wherever disturbing foam is to be suppressed. This is e.g. in nonaqueous media such as tar distillation or petroleum processing.
  • the antifoam compositions according to the invention are particularly suitable for controlling foam in aqueous media, preferably in aqueous surfactant formulations, such as
  • the defoamer compositions according to the invention are suitable as constituents of liquid detergents, where they are distinguished by excellent compatibility and
  • compositions according to the invention have the advantage that they are easy to handle as defoamers, are miscible with concentrated surfactant formulations, and that they are distinguished by a high, long-lasting effectiveness in a wide variety of media with small amounts added. This is extremely beneficial both economically and ecologically.
  • the determination of the viscosity of the individual components and of the antifoam compositions is carried out in accordance with DIN 53019-1 (2008-09), DIN 53019-2 (2001-02) and DIN 53019 (2008-09) with a cone and plate viscometer at 25 ° C. and a shear rate of 1 / s.
  • Liquid detergent given in Table 2 respectively specified amounts of defoamer formulations. Tolerability was visually assessed after 14 days of storage at 40 ° C.
  • the average foam height is called
  • Defoamer compound AI is SILFOAM® SC 1132 commercially available from Wacker Chemie AG München, this compound is based on
  • Defoamer compound A2 (not according to the invention, no component (a1) having aromatic radicals bonded directly to the Si atom) Defoamer compound A2 was prepared as follows:
  • Boiling range of 235-270 ° C (commercially available under the
  • Silicone resin comprising the units (by 29 Si-NMR and IR analysis): 40 mol% CH 3 SIOI / 2 - 50 mol% Si0 4/2 - 8 mol% C 2 H 5 OSi0 3/2 - and 2 mol% HOSi0 3/2 -, where this resin has a weight average molecular weight of 7900g / mol (based on
  • Defoamer compound A3 was prepared as follows:
  • Diorganopolysiloxane of 52 mol% 2-phenylpropenylmethysiloxane and 48 mol% dimethylsiloxane units having a viscosity of 2160 mPas obtained by reacting 139 g of a siloxane (CH 3 ) 3 -Si-O- [SiH (CH 3 ) -O] 40 - [Si (CH 3 ) 2 -O] 37 -Si (CH 3 ) 3 with 126 g of alpha-methylstyrene (2-phenylpropene) in the presence of a platinum catalyst), 5 parts of a fumed silica having a BET surface area of 300 va 2 / g (available under the name HDK ® T30 from Wacker Chemie AG Kunststoff), 10 parts one
  • Dissolver mixed and heated to 150 ° C for 4 hours. A creamy defoamer was obtained.
  • Defoamer compound A4 (not according to the invention, no component (a1) having aromatic radicals bonded directly to the Si atom)
  • Silicone resin comprising the units (by 29 Si-NMR and IR analysis): 40 mol% CH 3 SIOI / 2 - 50 mol% Si0 4/2 - 8 mol% C 2 H 5 OSi0 3/2 - and 2 mol% HOSi0 3/2 -, where this resin has a weight average molecular weight of 7900g / mol (based on
  • Polystyrene standard), and 0.7 part of a 20% by weight methanolic OH were mixed with a dissolver and heated to 150 ° C for 4 hours. There was obtained a defoamer with a viscosity of 8710 mPas.
  • Defoamer compound A5 was prepared as follows:
  • Hydrocarbon mixture (DI) with a boiling range of 235-270 ° C (commercially available under the name Exxsol D 100 S at Staub & Co Nuremberg, Germany), 5 parts of a
  • Room temperature solid silicone resin consisting of the following units (according to 29 Si NMR and IR analysis): 40 mol% CH 3 Si0 1/2 -, 50 mol% Si0 4/2 -, 8 mol% C 2 H 5 OSi0 3/2 - 2 mol% and HOSi0 3 2 -, wherein said resin has a weight average molecular weight of 7900g / mol
  • Defoamer compound A6 was prepared as follows:
  • R is a mixture of methyl and butyl radical
  • Defoamer compound A7 was prepared analogously to A6, except that 60 parts of silicone oil and 25 parts of silicone resin were used.
  • a defoamer with a viscosity of 2320 mPas was obtained.
  • Defoamer compound A8 was prepared as follows:
  • B2 A polypropylene glycol-polyethylene glycol copolymer with 10% polyethylene glycol and a viscosity of about 350 mPas
  • the polyether-modified sioxane (Cl) used for the formulations is a branched polyethersiloxane which, according to EP 1885770 Bl, paragraph [0083-0084], embodiment (B),
  • Polymer 1 has a viscosity of 5490 mPas at a shear rate of 1 / s.
  • the non-inventive defoamer compositions according to the comparative experiments V2 to V4 contain an organopolysiloxane in which the aromatic hydrocarbon radicals are not bonded via a ring carbon atom directly to the Si atom, but via an aliphatic hydrocarbon radical.
  • Table 1 shows that non-inventive defoamer compositions V2 to V4 are inhomogeneous and have phase separation so that they are unsuitable for use as defoamers.
  • the antifoam compositions according to the invention according to Examples 1 to 6 are homogeneous compositions, which is a prerequisite for their use as antifoams in liquid detergents.
  • defoamer formulation V5 according to the invention which contains no component (B), ie no polypropylene glycol or polypropylene glycol-polyethylene glycol copolymer,
  • Defoamer in liquid detergent have, in contrast to the non-inventive defoamer formulations VI and V5, which have a significantly worse defoaming effect especially after storage of the defoamer in the liquid detergent.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
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  • Medicinal Chemistry (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

L'invention concerne de nouvelles compositions d'un agent antimousse contenant (A) un composé antimousse contenant (a1) au moins un composé organosilicié qui comprend des motifs de la formule Ra (R1O) bR2 cSiO(4-a-b-c)/2 (I), dans laquelle R et R1 ont la signification indiquée dans la revendication 1 ; R2 signifie un reste d'hydrocarbure monovalent, le cas échéant substitué, aromatique qui est relié à l'atome de Si par un atome de carbone nucléaire ; a, b et c signifient respectivement 0, 1, 2 ou 3 sous réserve que la somme a+b+C ≤ 3 et, dans un 1 à 100 % de tous les motifs de la formule (I), c est différent de 0 et, dans au moins 50 % de toutes les unités de la formule (I), la somme a+b+c est égale à 2, (a2) est au moins une substance additive sélectionnée parmi (a21) des particules de charge et/ou (a22) une résine organopolysiloxane composée de motifs de la formule R3 d (R4O) eSiO(4-d-e)/2 (II), dans laquelle R3, R4, d et e ont la signification indiquée dans la revendication 1, la somme d+e≤3 et, dans moins de 50 % de toutes les unités de la formule (II), la somme d+e est égale à 2, et le cas échéant (a3) un composant organosilicié, qui comprend des motifs de la formule R5 g (R6O) hSiO(4-g-h)/2 (III), dans laquelle R5, R6, h et g ont la signification indiquée dans la revendication 1, la somme g+h≤3 et dans au moins 50 % de toutes les unités de la formule (III) la somme g+h est égale à 2, (B) des polypropylènes glycols et/ou des polypropylènes glycols/des copolymères de polyéthylène glycol, qui peuvent être à l'état final éthérifiés ou estérifiés ou, le cas échéant (C) des siloxanes modifiés au polyéther, le cas échéant (D) des composés organiques, et le cas échéant (F) d'autres additifs.
PCT/EP2017/053946 2016-03-01 2017-02-21 Composition d'un agent antimousse pour un détergent WO2017148750A1 (fr)

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EP17707502.5A EP3423165B1 (fr) 2016-03-01 2017-02-21 Compositions d'agent antimousse pour détergents
KR1020187025075A KR102142380B1 (ko) 2016-03-01 2017-02-21 세제용 소포제 조성물
CN201780014634.4A CN108778443B (zh) 2016-03-01 2017-02-21 用于清洁剂的消泡剂组合物
US16/081,789 US10870732B2 (en) 2016-03-01 2017-02-21 Defoamer compositions for detergents
JP2018545958A JP6816159B2 (ja) 2016-03-01 2017-02-21 洗剤用の消泡剤組成物

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DE102016203344.1A DE102016203344A1 (de) 2016-03-01 2016-03-01 Entschäumerzusammensetzungen für Waschmittel

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US10836981B2 (en) * 2017-11-10 2020-11-17 The Procter & Gamble Company Anti-foam compositions comprising an organopolysiloxane with adjacent hydrolysable groups
CN109432831B (zh) * 2018-11-07 2021-05-18 广州碧驰新材料股份有限公司 复合消泡剂及其制备方法
EP3848107B1 (fr) * 2020-01-08 2022-06-22 Evonik Operations GmbH Formulation et son utilisation en tant qu'agent antimousse
WO2021167728A1 (fr) * 2020-02-20 2021-08-26 Dow Silicones Corporation Composition de commande de mousse
CN113577840A (zh) * 2021-08-09 2021-11-02 杭州撒拉弗科技有限公司 一种耐高温、耐碱的有机硅消泡剂的制备方法
WO2023180637A1 (fr) 2022-03-21 2023-09-28 Elkem Silicones France Sas Emulsion concentrée d'antimousse silicone

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EP3423165A1 (fr) 2019-01-09
CN108778443A (zh) 2018-11-09
DE102016203344A1 (de) 2017-09-07
KR102142380B1 (ko) 2020-08-10
JP2019509887A (ja) 2019-04-11
JP6816159B2 (ja) 2021-01-20
KR20180107208A (ko) 2018-10-01
US10870732B2 (en) 2020-12-22
US20200165393A1 (en) 2020-05-28
CN108778443B (zh) 2021-10-29

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